Hydrogenating unsaturated organic material.



c. ELLIS. HYDROGENATING UNSATURATED ORGANIC MATERIAL.

APPLICATION FILED APR.24. 1912.

1 138 291, Patented May 4, 1915.

. ,Et'yl.

WITNESSES & INVEN'I'OR vww W earn er CARLETON ELLIS, OF MONTCLAI R, NEWJERSEY.

HYDROGENATING UNSATURATED ORGANIC MATERIAL.

To all whom it may concern Be it known that I, CARLn'roN ELLIS, acitizen of the United States, and a resident of Montclair, in the countyof Essex and State of New Jersey, have invented certain new and usefulImprovements in Hydrogenating Unsaturated Organic Material, of

which the following is a specification.

This invention relates to the process of hydrogenation of unsaturatedorganic bodies, such as hydrocarbon oils and fatty material in thepresence of catalytic bodies capable of carrying hydrogen to suchorganic compounds and relates in particular to the use of volatilecatalyzers, or catalyzers which acquire their active properties only byheating in a predetermined manner, such catalytic compounds preferablybeing of the nature of nickel carbonyl, and similar volatile bodies,preferably of an oil-soluble character.

Inthe present invention it is particularly the object to provide acatalytic body which is capable of being decomposed by heat in thepresence of an oil or similar substance to be treated and in thepresence of hydrogen or hydrogen containing gas, whereby metal licnickel or other similar material, in a very.

finely divided form, or even in a nascent condition, is secured.

Processes heretofore suggested for the treatment of oil with hydrogen inthe presence of catalyzers, have been concerned with catalyzers of anon-volatile character, such for example as nickel which has beenreduced from its oXid by treatment with hydrogen. It is difiicult toprepare a nickel catalyzer in this way because slight variations in thetemperature, when reducing the nickel oxid by hydrogen gas seeminglycause variations in the physical character and activity of the reducednickel. In the present invention, in its preferred form, nickel carbonylis used, and this is a potential catalyzer in that it decomposes onheating to form a suitable catalytic body.

Nickel carbonyl is readily prepared by passing carbon-monoxid overfinely divided nickel at a temperature of from 50 to 100 C. Thiscompound, as is weltknown, is volatile' and mixes readily with gases,such as carbon-monoxid and hydrogen. When heated in the air, it is veryquickly decomposed and is also affected by moisture. In.

the absence of air, it is decomposed by heating to a temperature of 200(3., or even less I Specification of Letters Patent.

Application filed April 24, 1912.

Patented May a, 1915.

Serial No. 692,903.

and when so decomposed by heat, the nickelis set free in a very finelydivided form. Nlckek carbonyl is readily soluble in many oily bodies,which is a property useful in the treatment .of many of the unsaturatedhydrocarbons or the fatty oils referred to.

In carrying out the present invention I preferably mix thenickel'carbonyl with hydrogen gas, or water gas, or other gas suitablefor the purpose and pass this mixture into an oil or other organic bodyto be treated. The oil is maintained at the decomposition temperature ofthe nickel carbonyl and also, preferably, at a temperature suited forrapid hydrogenation. Thus, the catalyzer 1s liberated in intimatecontact with hydrogen gas, thereby efiecting a rapid hydrogenation ofthe oil. The oil may contain, if desired, finely divided solid material,such as fullers earth and the like, to serve as an at taching base forthe deposited or separated nickel; but the use of such solid material isoften undesirable and the nickel in its nascent form liberated byheatdecomposition and in the absence of solid material to which it maybecome attached, is usually more desirable. In case the nickel forms acolloid,

which is not readily removed by filtration,

the oil may be boiled with an aqueous acid solution, to remove suchnickel material,

after it has served its purpose.

When treating material of a volatile na ture the mixture of hydrogen andnickel carbonyl may be caused to mingle with vapors of the volatile bodyand pass through a heated tube, or heated in any other suitable way, toconvert the vaporized potential catalyzer into an active nascentcatalyzer. In' this way various unsaturated fatty acids may be treated,using diminished pressure in order to form the vapors of such fattymaterial without producing any material amount of tarry bodies. Fattyesters, such as corn and cotton-seed'oil, soya bean oil, fish oil,almond oil, peanut and mustard oils, castor oil, linseed oil, ChineseWood oil and the like, are best treated in the liquid form.

A variety of low grade greases may be treated in this way to deodorizeand improve their consistency. Among these may be mentioned sewer andgarbage grease and under certain conditions cotton seed oil foots, Thesegreases may be treated at the oils, colored bodies are best secured isfirst desirable to'heat the oilito "the temperature of decomposition of.the nickel carbonyl, introducing the amount "of the latter requiredwith the first portion of hydronickel catalyzer.

gen gas-brought into contact with the oil. In this way an active nascentcatalyzing material is produced and the oil may then be quickly cooledto a temperature betteg suited for the hydrogenating step proper.

The oil is preferably gently stirred during the process ofhydrogenation, so as to bring about more uniform treatment. Violentagitation is not however necessary, owing to .the peculiar activeroperty of the nascent he process is best conducted by using oilwhich-has been freed from all traces of moisture and carefully dryingthe hyrogen gas before use.

As stated, it is desirable to regulate the temperature ofdecomposition'of the nickel compound according to the particularconditions of treatment, varying this according" to the oil employed andaccording to the pressure of the hydrogen gas. In some cases, asindicated, it is desirable to decompose the potential catalyzer at asomewhat higher temperature than that needed for completion of thehydrogenation. I

In addition to ni kel carbonyl, other volatile bodies having potentiallycatalytic p'roperties, including "the corresponding compounds of ironand the like, and some of the compounds ofthe metals with h'ydrocarbons,such for example as the methyl compounds of mercury, zinc, tin,thallium, lead and the like, may be employed.

The accompanying drawings showy-in a diagrammatic way, apparatussuitable for carrying out the present invention.

The drawings show the apparatus mainly in vertical section.

Like reference characters denote like parts.

In the drawing, 1 is a closed receptacle and mixing chamber having theagitator 2 which carries the cantedpropeller blades 3. The receptacleispartially jacketed by the jacket 4, into which steam or other heatingagent may be introduced.

5 is an inlet pipe foradmitting the oily body or other material to betreated to the rece tacle. This pipe carries the valve 6.

7 is an outlet pipe for the withdrawal of the treated oil and carriesthe .valve 8.

9 is an inlet pipe for the admission of hydrogen gas and the potentialcatalyzer. In the Figure 1, this is shown entering the tank from above,while in Fig. 2, the inlet pipe enters fromthe under side of thereceptacle. 10 is a mixing chamber where the hydrogen, orhydrogen-containing gas is mixed with the volatile catalyzer. In Fig. l,a heating apparatus for preheating the hydrogen, 11, is shown. The pipe12, having the valve 13, extends to the mixing chamber 10 and serves forthe admission of the hydrogen gas thereto. The pipe 14, having. thevalve 15, serves for the admission of the catalytic body, as for examplenickel carbonyl in a liquid or vaporized form. In Fig. 1, a receptacle16, having an inlet pipe 17, carrying the valve 18, serves as a closedcontainer for the volatile catalyzer. The pipe 19, having the valve 20,is an outlet, or blow-ofi'. In the receptacle are rods, or plates, shownas 21,- projecting from the Fig. 2, shows the stirrer, 2, carrying gascollectors, 22. These increase progresslvely in I hydrogen is admittedby the pipe-12, to the preheater 11, and passed to the vaporizer 10. Thecatalytic'material, or potentially active material, is admittedgradually by the pipe 14 to the receptacle 10. The mixture of thehydrogen gas and the potentially active material passes by the pipe-9into the receptacle 1, which is nearly filled with oil or other materialto be treated. The contents of the receptacle are preferably previouslheated to a temperatureof 150 to 200 by means of the heating jacket 4.The agitator is put in motion and the oil gently walls of the receptacleand serving as baflies. T

agitatedwhile the hydrogen gas mixture is 5 admitted to the receptacle.This agitation, which is continued for a substantial period of time,preferably for an hour or more according to the degree of hydrogenationrequired, insures a prolonged intimate contact of the hydrogen gasmixture with the material under treatment. After hydrogenation iscomplete, the treated oil is withdrawn from the pipe 7 In Fig. 2, whichrepresents the preferred form of the present invention,

the operation is substantially the same, but

the hydrogen mixture is admitted from the bottom and collects under thelowest gas chamber or bell. When this is filled the gas passes to thesecond chamber or bell and so 'on, filling each of-the bells with thegas and catalyzer.

Thus the catalyzer is distributed, as it were, as a plurality of layerswithin the body of the oil and ample time of contact is thusreadilysecured to enable its complete decomposition. The temperature L.

maintained in the receptacle is suificient to decompose the catalyzer,which in the case of nickel carbonyl, may often separate to a largeextent as a finely divided coating on or near the surface of the oil inthe several bells. By means of the pipe 19 and the valve 20, the spentgases may be removed eitherintermittently or continuously, as desired,and similarly, the hydrogen gas, carrying its charge of mckel carbonylor other volatile catalyzer may be admitted either I intermittently orcontinuously to the treating receptacle, according to the adjustment ofthe several valves, as is obvious.

As an illustrative-example of the process of the present invention, onemay place in the receptacle a charge of, say, cotton seed oil and heatto a temperature of about 180 C. A quantity of nlckel carbonyl,equivalent to about 1% or so of the weight of the oil is mingled withhydrogen gas and brought into contact with the oil with gentle agitationfor a period of an hour or more according to the degree of hydrogenationrequired. Thus the nickel carbonyl is confined in contact with the oilfor a protracted period which allows of its complete decomposition. Inaccordance wlth the oil to be treated,

the pressure'of the hydrogen may vary from below atmospheric up to apressure of 10 lbs. to 25 lbs. to the square inch, or higher.

This application is a divisional continuation in part of Serial No.688,814, filed April 5, 1912.

'What I claim is,

The process comprising adding nickel carbonyl and'hydrogen tounsaturated fatty material, subjecting the mixture to a predeterminedtemperature suflicient t0 decompose the nickel carbonyl and cause theresulting nickel and the hydrogen to react upon the unsaturated fattymaterial and completing the hydrogenation at a lower temperature.

Signed at Montclair in the county of Essex and State of New Jersey, this22nd day of April, 1912.

CARLETON ELLIS.

Witnesses:

BIRDELLA M. ELLIs, THos. F. RocHE.

